Detergent briquette



Patented Aug. 22, 1950 DETERGENT BRIQUETTE James Douglas MacMahon, Niagara Falls, N. Y., assignor to Mathleson Chemical Corporation, a corporation of Virginia No Drawing. Application July 21, 194 5,

Serial N0. 606,482

4 Claims. (Cl. 252-137) This invention relates to improved briquetted detergent compositions having desirable physical,

and chemical properties and which, in addition to imparting desirable detergent properties to the washing solution in which they are used, also impart bactericidal or bacteriostatic properties to said solution.

The briquettes of my present invention are unique in their combination of detergent and bacteriotoxin characteristics and other physical and chemical properties which make them highly satisfactory for use in modern mechanical washing operations.

In my co-pending applications, Serial No. 429,127, Serial No. 429,128 and Serial No. 429,129, on which Letters Patent 2,382,163, 2,382,164 and 2,382,165 respectively were issued August 14, 1945, I have described and claimed detergent briquettes consisting of dense crystalline aggregates of relatively uniform composition which are hard, strong and physically stable, being capable of withstanding the conditions of shipment and storage essential to ultimate commercial use without material deterioration, disintegration of deliquescence, and which do not disintegrate under normal conditions of use. The briquettes there described have uniform solubility rates, and there is no objectionable chemical change in the composition of the briquette. Further, said briquettes can be produced without resort to high temperatures, and the congealing and hardening time of these briquettes during molding is sufliciently rapid to permit their economical commercial production.

My present invention is applicable to briquettes of the type therein described, and is predicated upon my discovery that effective proportions of certain cationic disinfectants may be incorporated in such briquettes without detrimentally affecting the physical properties, the chemical stability, or the detergent characteristics of the ,briquette.

The disinfectant constituents contemplated by .my present invention are the quaternary ammonium compounds which contain in the cation 9. pentavalent nitrogen atom having four valence bonds satisfied in the cation by organic radicals, one of which bonds is either directly or indirectly attached to an alkyl radical containing not less than 8 carbon atoms. The number of carbon atoms in the said alkyl radical may vary over a considerable range, say up to about 20-22 carbon atoms. Such quaternary ammonium compounds have previously been known to possess powerful germicidal properties.

Nitrogen compounds of this type include variousquaternary ammonium compounds in which the anion is a halogen, nitrate,v sulfate, methosulfate, or other similar anion. Of these, the

halides have been found to be particularly desirable.

These quaternary ammonium compounds, contemplated by my present invention, may be represented generally by the structural formula:

where N is nitrogen; X is the anion, for instance a halide 0r nitrate; R1 and R2 are lower alkyl groups advantageously containing less than 4 carbon atoms, and which may be like or different; R3 may be a similar type of alkyl group, or may be an aralkyl group advantageously containing 8 to 12 carbon atoms, which may or may not be substituted by hydroxyl radicals or halogen; and R4 is an alkyl radical, such as previously described, containing not less than 8, and usually not more than 18, carbon atoms. Also, R4 may be a complex radical containing an alkyl or aralkyl group interrupted by oxygen or sulfur. In one such compound, which has been found to be particularly effective, the alkyl portion of this complex radical is a di-isobutyl group.

The quaternary ammonium compounds contemplated by my present. invention also include those containing a heterocyclic radical, in which two or three of the four bonds satisfied in the cation are connected into a heterocyclic radical, for instance pyridine, quinoline, iso-quinoline or piperidine, and one of the other bonds within the cation is satisfied by an alkyl radical such as described above. Where only two of these bonds. are connected into the heterocyclic radical, the remaining cationic bond may be satisfied by a lower alkyl radical, such as just described.

Examples of such quaternary ammonium compounds are cetyl trimethyl ammonium bromide, lauryl dimethyl benzyl ammonium chloride, cetyl dimethyl benzyl ammonium chloride, cetyl dimethyl ethyl ammonium bromide, lauryl pyridinium chloride, cetyl pyridinium bromide, lauryl isoquinolinium bromide, lauryl methyl piperidinium chloride, and paratertiary-octyl-phenoxyethoxy-ethyl dimethyl benzyl ammonium chloride monohydrate. v

As previously'noted, my present invention is applicable to briquettes of the type described in my Patent 2,382,163, which consist essentially of the following ingredients and proportions thereof by weight within the respective indicated ranges: trisodium phosphate, about 1-15%, sodium silicate, in which the NazO S102 ratio is not less than 1:1 nor greater than 2:1, about l-25%, sodium carbonate, about 20-50%, water about 30-40%, and tetrasodium pyrophosphate about 3-25%.

My present invention is also applicable to briquettes of the type described in my Patent 2,382,165, as previously-noted, which consists essentially of the following ingredients in proportions by weight within the following respective indicated ranges: trisodium phosphate about 145%, sodium silicate, in which the NaaO S: ratio is not less than 1:1 nor greater than 2:1, about 1-25%, soda ash about 10-50%, water about 30-40%, and about 1-20% of sodium hexametaphosphate or sodium tetraphosphate.

The invention is likewise applicable to briquettes of the type described in my previously noted Patent 2,382,164, which consist essentially of the following ingredients in proportions by weight within the respective indicated ranges: sodium silicate, in which the NazO S10: ratio is less than 1:1, about 1-20%, water about 30-40%, and at least one detergent of the group consisting of sodium carbonate and trisodium phosphate, aggregating from about one-fourth to one-half the total formula weight.

My present invention is likewise applicable to briquettes of the type described in my Patent 2,412,819, which consist essentially. of the following ingredients in proportions by weight within the respective indicated ranges: sodium silicate, in which the NazO S102 ratio is not less than 1 nor greater than 2, about 1-l5%, water about 30-50%, sodium tripolyphosphate about 2-50%, and at least one detergent of the class consisting of trisodium phosphate and sodium carbonate, aggregating from about one-tenth to about onehalf of the total formula weight.

The present invention is likewise applicable to briquettes of the type described in my Patent 2,444,837, which consists essentially of the following ingredients in proportions by weight within the respective indicated ranges: total water about 30-50%, at least one detergent of the group consisting of sodium carbonate and trisodium phosphate aggregating from about one-tenth to about one-half the total formula weight and about 1-30% of a sodium borate.

The present invention is likewise applicable to certain briquettes of the general type previously described herein which is substantially free from sodium silicate and which consists essentially of the following ingredients in proportions by weight within the respective indicated ranges: total water 30-50%, at least one detergent of the group consisting of sodium carbonate and trisodium phosphate aggregating from about one-tenth to about one-half the total formula weight, and at least one polyphosphate of the group consisting of tetrasodium pyrophosphate, sodium tripolyphosphate, sodium tetraphosphate and sodium hexametaphosphate, aggregating about 23-50% but not exceeding about of sodium tetraphosphate or sodium hexametaphosphate.

The briquettes of my present invention have substantially the same physical structure as the briquettes just described, and by a proper selection of the prescribed ingredients and proportions thereof, briquettes having a wide range of detergent properties may be produced to suit particular detergent operations. However, the briquettes of my present invention have the added advantage of imparting bacteriacidal or germicidal properties to the wash water.

Though is was known that these quaternary ammonium compounds have powerful germicidal properties, it was not to be expected that these complex, highly active materials would be compatible with the other constituents of these briquettes under the necessary briquctting conditions, and further it could not be foreseen that these quaternary ammonium compounds could be incorporated in briquettes of the types herein described without materially influencing detrimentally the physical properties of the briquettes.

The problem presented involves not merely the production of a material or mixture of materials having the desired detergent and bacteriotoxin characteristics, but also requires the development of a product which in addition to meeting those requirements can be economically produced in the form of briquettes having physical properties essential to their use in modern mechanical washing operations, including physical stability, strength, and uniform-solubility rates.

The detergent mixtures of which may improved briquettes are composed may be prepared by mixing the previously noted ingredients in proportions within the indicated ranges for the particular type of briquette desired, as hereinafter more fully described and illustrated. In the preparationof the briquette it must be kept in mind that though a wide range of ingredients and pro- 7 portions thereof is permissible, these ranges are steam-jacketed kettle equipped with a stirring device. I have obtained excellent results in preparing and in duplicating the structure of the briquettes by adhering to the following procedure: The predetermined amount of water glass and caustic soda, or of the particular sodium silicate desired, trisodium phosphate, borate and water, or such of these materials as are to be used, are placed in the kettle and heated with constant agitation until the mass is fluid. The temperature is then maintained below that at which substantial evolution of steam would occur with the resultant loss in water content. Higher temperatures than necessary are to be avoided, as it is desirable to reduce to a minimum the amount of water lost during the heating operation. The temperature to which the material is heated, and at which it is held, depends primarily upon the concentration of the solution in the fluid mass, and is usually found to be within the range of about 70 C. to about C. The fluid mass is held at this temperature until maximum clarity is obtained. This usually requires from 10 to 20 minutes, depending upon the composition and amount of solution.

After clarification of the mass, a predetermined amount of soda ash is then added, if this constituent is to be used, and thoroughly mixed with the fluid mass. If the addition of soda ash results in a decrease in temperature, and the mass becomestoo viscous for final pouring, the temperature may be increased until adequate fluidity is obtained, care being taken to avoid temperatures which result in the material loss of water.

The polyphosphate when used is advantageously added and thoroughly mixed into the mass in the kettle just prior to pouring. Generally at this point in the operation, the temperature of the mass should be at a minimum for adequate pouring fluidity. However, when the polyphosphate used is in a slowly soluble form, particularly where sodium pyrophosphate is used, it may with advantage be added prior to the addition of the soda ash.

The quaternary ammonium compound is with advantage added to the fluid mass and thoroughly admixed therewith just prior to withdrawal from the kettle.

The mixture is finally drawn off into suitable molds and allowed tocongeal until the briquette has developed suflicient mechanical strength to permit its removal from the mold. The necessary molding time will generally vary from about one hour to several hours, depending upon the composition of the mixture.

On cooling, detergent compositions of this type seem to expand somewhat, and this, combined with the tendency to adhere to metal surfaces of the molds, has previously presented considerable difliculty in the molding of detergent materials. I have found that by using flexible molds, such as molds made of rubber or similar material, these difliculties are eliminated.

The amount of water present in the detergent composition is of major importance, as previously noted, with respect to molding time, and also their detergent capacity. It is essential that suflicientwater be present during the process to produce under processing conditions a mass suiilciently fluid to permit satisfactory mixing and pouring into the molds, and have satisfactory molding characteristics. However, the addition of an excess of water is generally to be avoided since the processing normally does not involve conditions under which excess water would be eliminated.

I have previously indicated the permissible range of proportions of water in the respective types of briquettes. Proportions of water in the product up to the maximum amounts indicated do not materially increase the congealing time or detrimentally affect the physical structure of the briquettes. However, a proportion of water in excess of the indicated maximums has been found to increase the molding time to impracticability and to afiect disadvantageously uniformity of structure of the resulting briquettes. When the water content much exceeds these upper limits, there is a tendency toward segregation during the congealing period. Usually more satisfactory results are obtained where the proportion of water is not much in excess of that required to give suillcient fluidity for molding.

In determining the quantity of water, if any, to be added as such in the compounding operation, due consideration must be given to the amount of water present in the various constituents, either as water of crystallization or otherwise, and of water formed by chemical reactions.

In compounding my briquettes, the trisodium phosphate, when used, may be introduced in the form of ordinary commercial dodecahydrate generally represented by the formula NaaPO4.12H2O "Theoretically, this material contains 56.8% of water, The proportions of such material given herein are based upon the anhydrous product. Trisodium phosphate of lower water content than the dodecahydrate may be used, provided appropriate compensation be made for the proportion of water contained therein.

Materials which react under the process conditions to form trisodium phosphate, for instance disodium phosphate and caustic soda. may be substituted for equivalent proportions of trisodium phosphate.

The sodium carbonate may conveniently be added as anhydrous soda ash. However, it may be supplied in the form of hydrates such as mono-'- or dodecahydrates, j appropriate allowances being made for differences in composition. Similarly, the polyphosphates are preferably supplied in the usual anhydrous forms and proportions thereof appearing herein have reference to such anhydrous materials.

As previously indicated, the sodium silicate constituent, when used, may be added as sodium silicate of the desired alkalinity, or, in lieu of such silicate, one may add water glass and a sumcient amount of caustic soda to produce the sodium silicate of the desired alkalinity.

The quaternary ammonium compounds have been found generally to be incompatible with compounds having high molecular anions, such as higher alkyl sulfates and high molecular sulfonates. It is therefore generally inadvisable to include the latter types of surface active agen in the briquettes of my present invention.

The proportion of the quaternary ammonium compound used in accordance with my present invention may vary over a considerable range. The optimum proportion depends primarily upon the germicidal potency of the particular quaternary ammonium compound used, upon the use for which the briquette is intended, and upon the extent of the germicidal or bacteriocidal action relative to the detergent action required.

Some of the quaternary ammonium compounds have a germicidal potency of such a degree that dilutions as great as 1 part in 50,000 parts will arrest the growth of bacteria, and dilutions as great as 1 part in 5,000 parts will exert a powerful germicidal eifect. All are very potent and accordingly only minor proportions are ordinarily required in the briquettes.

The optimum proportions of quaternary ammonium compound to be used, with respect to the molding characteristics of the briquette, appear to depend to some extent upon the composition of the particular briquette. In general, it has been observed that the inclusion of these quaternary ammonium compounds has a tendency to increase the molding time. In those types of briquettes previously described, which contain no sodium silicate or borate or where those constituents are present only in amounts approaching the minimum of the prescribed ranges, it is possible to incorporate a somewhat higher proportion of the quaternary ammonium compound without any noticeable tendency to affect adversely the molding characteristics of the briquette than in those types of briquettes containing larger proportions of sodium borate or sodium silicate, particularly the borates and silicates of higher alkalinity. I have usually found that the tolerance exhibited toward the inclusion of the quaternary ammonium compounds in the briquettes is increased by the presence of tetrasodium pyrophosphate or sodium tripolyphosphate in the composition, and decreased by large proportion: of trisodium phosphate.

' Just described, this proportion may be increased up to at least Though any proportion of the quaternary ammonium compound not exceeding that which ob- ,iectionably interferes with the molding properties of the briquette may be used, the minimum practical amount depends generally upon the desired germicidal properties of the resultant briquette, upon the potency of the particular quaternary ammonium compound used, and upon the concentration of the detergent solution required for any specific cleansing operation.

For example, if a particular quaternary ammonium compound on a dry basis will induce bacteriostasis at a dilution of 1 part to 25,000 parts, and a concentration of the briquette composition of 1 part in 500 parts of water is all that is required for a particular cleansing operation, it

. will be necessary to include 2% of the particular quaternary ammonium compound in the briquette. On the other hand, if the selected quaternary ammonium compound will arrest the growth of bacteria at a dilution of 1 part to 50,000 parts of solution, and a concentration of the briquette composition of 1 part in 100 parts of solution is required for the cleansing operation, then the proportion of the quaternary ammonium compound included in the briquette need be only 0.2% of the briquette composition.

Consequently, it will be understood that a lower limit of the proportion of quaternary ammonium compound to be used in the briquette cannot definitely be established for all purposes. But in the light of existent knowledge regarding detergent solution requirements, and the degree of germicidal effectiveness of the quaternary ammonium compounds, a minimum proportion of about 0.2 %-2% of the briquette composition may generally be considered as a commercially practical one.

The following analyses set forth in the table are presented as specific illustrations of the several types of briquettes which may be produced in accordance with my present invention. It will be understood, however, that my invention is not limited to briquettes of the particular compositions illustrated. In each instance the proportions are'by weight and are on an anhydrous basis.

Table 8 cats was 1:1, and in Example 10 this ratio of the silicate was greater than 1:1.

In Examples 1, 2, 8, 4, 8, 9, and 11, the particular quaternary ammonium compound used was cetyl dimethyl benzyl ammonium chloride. In Examples 5, 7 and 10, lauryl dimethyl benzyl ammonium chloride was used, and in Example 6, cetyl trimethyl ammonium bromide was used as the quaternary ammonium'compound.

These quaternary ammonium compounds are generally stable in alkaline environments such as those encountered in the briquettes herein described and under the detergent conditions for which these briquettes are normally used. However, they vary somewhat in their stability in strongly alkaline environments. For this reason, precaution should be taken to select a quaternary ammonium compound which is known to be stable under the conditions of alkalinity of the particular briquette in which it is to be incorporated.

I claim:

1. In a detergent briquette of the type which is physically stable, hard, strong and non-deliquescent, and consisting of a dense crystalline aggregate consisting essentially of the following ingredients in proportions by weight within the respective indicated ranges: trisodium phosphate about 1-l5%, sodium silicate, in which the NazO SiO: ratio is not less than 1:1 nor greater than 2:1, about l-25%, sodium carbonate about 20-50%, tetra sodium pyrophosphate about 3- 25%, and water about 30-40%, the improvement which comprises a briquette having said physical characteristics and said chemical composition further containing a quaternary ammonium compound containing an .alkyl radical of not less than 8 carbon atoms in an amount within the range of about 0.2% to about 10% on the total weight of the briquette.

2. In a detergent briquette of the type which is physically stable, hard, strong and non-deliquescent, and consisting of a dense crystalline aggregate consisting essentially of the following ingredients in proportions by weight within the respective indicated ranges: trisodium phosphate about 1-35%, sodium silicate, of which the NazO S10: ratio is not less than 1:1 nor greater than 2:1, about l-25%, sodium carbonate about 10-50%, total water about 30-40%, and a phosphate of the group consisting of sodium hexametaphosphate and sodium tetraphosphate, about 1-20%, the improvement which comprises a briquette having said physical characteristics and said chemical composition further contain- Tetra Sodium Pyrophosphate 'lri Sodium Phosphate Sodium Tripolyphos- Quin-ternary Ammonium Compound Total Water phate Example 1 Example 2 Example 3 GEE? Example 10 Example 11 Example 12 mongg F :9 I wave a- In Examples 3 and 11, the sodium silicate was one having a ratio of NazO $10: of less than 1:1. In Example 4, this ratio of the sodium siliing a quaternary ammonium compound containing an alkyl radical of not less than 8 carbon atoms in an amount within the range of about 0.2% to about 10% on the total weight of the briquette.

3. In a detergent briquette of the type which is physically stable, hard, strong and non-deliquescent, and consisting of a dense crystalline aggregate consisting essentially of the following ingredients in proportions by weight within the respective indicated ranges: total water 30- 50%, at least one detergent of the group consisting of sodium carbonate and trisodium phosphate aggregating from about one-tenth to about one-half the total formula weight, and at least one polyphosphate of the group consisting of tetrasodium pyrophosphate, sodium tripolyphosphate, sodium tetraphosphate and sodium hexametaphosphate, aggregating about -50% but not exceeding about 15% of sodium tetraphosphate and sodium hexametaphosphate, a briquette having said physical characteristics and said chemical composition further containing a quaternary ammonium compound containing an alkyl radical of not less than 8 carbon atoms in an amount within the range of about 0.2% to about 10% on the total weight of the briquette.

4. In a detergent briquette of the type which is physically stable, hard, strong and non-deliquescent, and consisting of a dense crystalline aggregate consisting essentially of the following ingredients in proportions by weight within the respective indicated ranges: total water 30 to 50%, at least one detergent of the group consisting of sodium carbonate and trisodium phosphate aggregating from about one-tenth to about one-half the total formula weight, a detergent of the group consisting of sodium silicate and sodium borate where the silicate aggregates from about 1 to 25% and the borate aggregates about 1 to 30%, and at least one polyphosphate of the group consisting of tetrasodium pyrophosphate, sodium tripolyphosphate, sodium tetraphosphate and sodium hexametaphosphate, aggregating about 5 to but not exceeding about 15% of sodium tetraphosphate and sodium hexametaphosphate, the improvement which comprises a briquette having said physical characteristics and said chemical composition further containing a quaternary ammonium compound containing an alkyl radical of not less than 8 carbon atoms in an amount within the range of about 0.2% to about 10% on the total weight of the briquette.

JAMES DOUGLAS MACMAHON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS I Number Name Date 2,164,092 Smith June 27, 1939 2,175,781 Riggs et a1. Oct. 10, 1939 2,317,999 Teuchs May 4, 1943 

3. IN A DETERGENT BRIQUETTE OF THE TYPE WHICH IS PHYSICALLY STABLE, HARD, STRONG AND NON-DELIQUESCENT, AND CONSISTING OF A DENSE CRYSTALLINE AGGREGATE CONSISTING ESSENTIALLY OF THE FOLLOWING INGREDIENTS IN PROPORTIONS BY WEIGHT WITHIN THE RESPECTIVE INDICATED RANGES: TOTAL WATER 3050%, AT LEAST ONE DETERGENT OF THE GROUP CONSISTING OF SODIUM CARBONATE AND TRISODIUM PHOSPHATE AGGREGATING FROM ABOUT ONE-TENTH TO ABOUT ONE-HALF THE TOTAL FORMULA WEIGHT, AND AT LEAST ONE POLYPHOSPHATE OF THE GROUP CONSISTING OF SODIUM CARBONATE AND TRISODIUM PHOSPHATE AGGREGATING FROM ABOUT ONE-TENTH TO ABOUT ONE-HALF THE TOTAL FORMULA WEIGHT, AND AT LEAST ONE POLYPHOSPHATE OF THE GROUP CONSISTING OF TETRASODIUM PYROPHOSPHATE, SODIUM TRIPOLYPHOSPHATE, SODIUM TETRAPHOSPHATE AND SODIUM HEXAMETAPHOSPHATE, AGGREGATING ABOUT 5-50% BUT NOT EXCEEDING ABOUT 15% OF SODIUM TETRAPHOSPHATE AND SODIUM HEXAMETAPHOSPHATE, A BRIQUETTE HAVING SAID PHYSICAL CHARACTERISTICS AND SAID CHEMICAL COMPOSITION FURTHER CONTAINING A QUATERNARY AMMONIUM COMPOUND CONTAINING AN ALKYL RADICAL OF NOT LESS THAN 8 CARBON ATOMS IN AN AMOUNT WITHIN THE RANGE OF ABOUT 0.2% TO ABOUT 10% ON THE TOTAL WEIGHT OF THE BRIQUETTE. 